Two broadly applicable strategies for extending the available ligand platforms of the virtually unexplored terminal TiN–NR₂ functional group are described, along with the highly selective room temperature insertion of alkynes into the N–N bond of Ti{MeN(CH₂CH₂NSiMe₃)₂}(NNPh₂)(py) and the catalytic cis-diamination of PhCCMe by diphenylhydrazine.